JP2001117189A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material having high sensitivity, excellent in fog stability and having improved shelf stability. SOLUTION: The silver halide color photographic sensitive material has photographic constituent layers comprising at least two red-sensitive layers, at least two green-sensitive layers, at least two blue-sensitive layers and at least two non-photosensitive layers on at least one side of the substrate and contains a compound of the formula R1-(S)m-R2 and a chemically sensitized silver halide emulsion having 40-70 mV silver potential. In the formula, R1 and R2 are each an aliphatic group, an aromatic group, a heterocyclic group or a group of atoms which may form a ring by bonding to each other, when R1 and R2 are each an aliphatic group, they may bond to each other to form a ring, and (m) is an integer of 2-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in sensitivity, fog stability and storage stability.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) are said to be mature products with extremely high degree of perfection, while the required performance is high sensitivity, high image quality, and preservation. There is a wide variety of conditions, such as little performance fluctuation due to conditions, and it is necessary to take into account rapid processing suitability with faster development progress, and the required level has been increasing in recent years.

[0003] In particular, in terms of high sensitivity, due to the recent technological advancement of digital cameras, in order to maintain the superiority of silver halide photographic materials, it is necessary to keep fog low and to maintain compatibility with storage. Higher sensitivity is required.

Techniques for increasing the sensitivity of silver halide emulsions, that is, sensitization techniques, relate to a method for producing a silver halide emulsion, to chemical sensitization of a silver halide emulsion, to spectral sensitization of a silver halide emulsion, Various methods are known, such as a method for designing a silver halide light-sensitive material and a method for developing a silver halide light-sensitive material. Among them, the most preferable and essential method is the method of photosensitizing a silver halide crystal. The goal is to reduce inefficiencies in the process and improve quantum efficiency. One of the means is chemical sensitization, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization using a noble metal such as gold, reduction sensitization using a reducing agent, these Are used alone or in combination. Above all, when gold sensitization is used in combination with sulfur sensitization, selenium sensitization, and tellurium sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases. Especially gold?
Compared with sulfur sensitization, gold-selenium and tellurium sensitization have a particularly large fog increase, and there has been a demand for the development of a technique for suppressing the generation of fog, and a sensitization technique for reducing fog and sensitivity during storage.

It is known to use an inhibitor as a method for improving the fog, storage stability and the like of a silver halide light-sensitive material. For example, JP-A-5-53234 and JP-A-5-2736
Nos. 0, 5-19395, 5-17540 and the like disclose various combinations of inhibitors. However, improvement of fog and storage stability leads to desensitization and other problems. Not reached. As an inhibitor having a mercapto group and a water-soluble group, Japanese Unexamined Patent Publication (Kokai) No. 2-837 discloses an agent for preventing fogging of tabular grains and improving low light intensity failure.
No. 16838 discloses an antifoggant for selenium sensitization. Also, JP-A-6-19024 and JP-A-6-19024.
19026 and 6-19037 disclose that a reaction-inactive chalcogen compound is effective in preventing fog.

[0006] The fogging problem involves two points: fog (absolute fog value) of the final silver halide emulsion itself introduced into the silver halide light-sensitive material and fog progression in the process of optimal chemical ripening. is there. A silver halide emulsion having a low absolute fog value is considered to be ideal from the viewpoint of the production stability, and the progress of fogging is preferably slow, and the photographic performance is not satisfactory.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent fog stability and improved storage stability.

[0008]

The object of the present invention can be achieved by the following inventions.

1. On one side of the support, a silver halide color photographic light-sensitive material having a photographic component layer consisting of at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, A silver halide color photographic material comprising a compound represented by the general formula (1) and a silver halide emulsion chemically sensitized at a silver potential of 40 to 70 mV.

Formula (1) R _1- (S) m-R _{2 In the} formula, R ₁ and R ₂ may each be an aliphatic group, an aromatic group, a heterocyclic group, or may be bonded to each other to form a ring. Represents a group of possible atoms. When R ₁ and R ₂ are an aliphatic group, they may combine with each other to form a ring. m represents an integer of 2 to 6.

2. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support. A silver halide color photographic light-sensitive material comprising a silver halide emulsion to which a sensitizing dye is added in a fine solid dispersion state and which is chemically sensitized at a silver potential of 40 to 70 mV.

3. In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least two red-sensitive layers, green-sensitive layers, blue-sensitive layers and non-light-sensitive layers on one side on a support, In the salting step, an aggregating polymer agent is added, and the processing temperature of the desalting step is set to 40 ° C. or more and the pH is set to 5.1 or less.
A silver halide color photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with V.

4. On one side of the support, a silver halide color photographic light-sensitive material having a photographic component layer consisting of at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, A compound represented by the general formula (2) is added during the respective addition periods of the spectral sensitizing dye and the chalcogen sensitizer, and contains a silver halide emulsion chemically sensitized at a silver potential of 40 to 70 mV. A silver halide color photographic light-sensitive material, characterized in that:

[0014]

Embedded image

In the formula, X represents N or CR ', and R' represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n is 0 or 1
Represents R ₃ and R ₄ -SO ₃ H, -COOH, -O
H and -NHR ₅ and having the at least one direct or indirect groups selected from their salts. R ₅ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group.

5. A silver halide color photographic material having at least one photographic constituent layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support, A silver halide emulsion containing 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol of alkaline earth metal per mol of silver halide and chemically sensitized at a silver potential of 40 to 70 mV. Silver halide color photographic material.

6. A silver halide color photographic light-sensitive material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support, It contains a compound represented by the general formula (1), and the compound represented by the general formula (2) is added between the addition times of the spectral sensitizing dye and the chalcogen sensitizer, and the silver halide 1 A silver halide containing 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol of an alkaline earth metal per mol, and containing a silver halide emulsion chemically sensitized at a silver potential of 40 to 70 mV. Color photographic light-sensitive material.

Hereinafter, the present invention will be described in detail.

The silver potential of the silver halide emulsion in the present invention refers to the silver potential of the silver halide emulsion before it is subjected to spectral sensitization and chemical sensitization. It can be determined by measuring with a silver ion selective electrode using a silver chloride electrode as a reference electrode. The silver potential of the silver halide emulsion in the invention is from 40 to 70 mV, preferably from 40 to 60 mV, and more preferably from 45 to 70 mV.
55 mV.

In the silver halide emulsion used in the present invention, 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is preferably tabular silver halide grains, more preferably 60%. %, More preferably 80% or more.

In the silver halide grains of the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is preferably 60% or more in terms of the number of silver halide grains. Preferably 70% or more, more preferably 8%
0% or more.

In the present invention, the tabular silver halide grains are silver halide grains having an aspect ratio of 1.3 or more. The aspect ratio is preferably from 3.0 to 100,
More preferably, it is 5.0 to 50.

To determine the aspect ratio, first, the diameter and thickness of silver halide grains are determined by the following method. A sample is prepared on a support in which a latex ball having a known particle diameter serving as an internal standard and a main plane are coated so as to be oriented parallel to the support, and shadowing is performed from a certain direction by a carbon vapor deposition method. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like, and the diameter / thickness of the projected area is referred to as an aspect ratio. At this time, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The twin plane of the silver halide grains can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1μ.
Obtain a thin section of about m. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The average grain size of the tabular silver halide grains in the present invention is preferably 0.2 to 20 μm, and 0.3 to 1 μm.
5 μm is more preferred, and 0.5 to 5.0 μm is most preferred.

In the present invention, the average particle size is the arithmetic average of the particle size ri. However, three significant figures and the least significant figure are rounded off, and the number of measured particles is indiscriminately 1,000 or more.

In the case of tabular silver halide grains, the diameter ri is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area. In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area.

The grain size ri can be obtained by photographing silver halide grains with an electron microscope at a magnification of 10,000 to 70,000, and then measuring the grain diameter or the projected area on the print.

As the silver halide emulsion of the present invention, any emulsion such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferred.

The monodisperse emulsion preferably has a particle size distribution of less than 20%, more preferably less than 16%, when the particle size distribution is defined by the following formula.

Particle size distribution (%) = (standard deviation of particle size / average particle size) × 100 The average particle size and standard deviation are determined from the particle size ri defined above.

In the silver halide emulsion of the present invention, any silver halide such as silver iodobromide, silver iodochlorobromide and silver iodochloride can be used. In particular, silver iodobromide and silver iodochlorobromide are preferred. The average silver iodide content of the silver halide grains contained in the silver halide emulsion is preferably 0.5 to 30 mol%, more preferably 1 to 20 mol%.

The average silver iodide content of the silver halide grains was determined by an EPMA method (Electron Probe Micror).
o Analyzer method). In particular,
A sample in which silver halide grains are well dispersed so that they do not come into contact with each other is prepared. The sample is irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and silver and iodine emitted from individual silver halide grains are produced. By determining the respective X-ray intensities, the silver iodide content of each of the silver halide grains can be determined. This is measured for at least 50 silver halide grains, and the average value thereof is determined.

As the silver halide grains contained in the silver halide emulsion of the present invention, core / shell type grains can also be preferably used. Core / shell particles are particles composed of a core and a shell covering the core,
The shell is formed by one or more layers. The silver iodide content of the core and the shell is preferably different from each other.

In the present invention, the outermost layer of the silver halide grains refers to a silver halide layer including the surface of the silver halide grains and having a depth of 5 × 10 ⁻³ μm from the surface of the silver halide grains. The average silver iodide content of the outermost layer of the silver halide crystal means an average of silver iodide contents measured at five or more places at equal intervals in the outermost layer of the silver halide grains. .

In the present invention, the average silver iodide content of the outermost layer of each of the main plane portion and the side surface portion of the silver halide grain is measured by the following method.

After the tabular silver halide grains in the silver halide emulsion are decomposed into gelatin using a proteolytic enzyme, the silver halide grains are embedded in methacrylic resin, and the thickness is reduced using a diamond cutter. Cut continuously as 5 × 10 ^-2 μm sections. Among these sections, in a sample in which a tomographic plane perpendicular to two parallel principal planes appears, the silver halide phase from the surface parallel to the principal plane to a depth of 5 × 10 ⁻³ μm was obtained. The region is defined as a main plane portion, and the outermost layer portion of the silver halide crystal other than the main plane portion is defined as a side surface portion. For the main plane portion and the side surface portion, the spot diameter was set to 5 × 10
^The silver iodide content is measured by spot analysis focused on ^-3 μm or less, preferably 2 × 10 ⁻³ μm or less.

The silver halide emulsion of the present invention, I ₁ mol% of average silver iodide content outermost layer of the silver halide grains in the main flat portion, when the I ₂ mol% in a side section, I _1> It is preferred that the tabular silver halide grains of I _{2 be} at least 50% (number). The relationship between I ₁ and I ₂ is preferably I ₁ / I ₂ > 1.3, more preferably I ₁ / I ₂ > 2.0, and I ₁ / I ₂ > 2.5. Is most preferred. Also, it is preferable that I ₁ is less than 30 mol%,
More preferably, it is less than 20 mol%.

The silver halide grains in the silver halide emulsion of the present invention preferably have dislocation lines therein.
There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The dislocation lines are introduced in the silver halide grains preferably in a region where the added position is 50% or more when the distance from the center of the silver halide grains to the surface is 100%.
% Is more preferably introduced into a region of not less than 85%. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and further preferably 80% or more. preferable. In each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and further preferably 30 or more.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton; Photo. Sci.
Eng. , 11 (1967) 57; Shioza
wa; Soc. Photo. Sci. , Japan
35 (1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature.
That is, the silver halide grains taken out carefully are placed on a mesh of an electron microscope so as not to apply a pressure enough to newly generate dislocation lines from the emulsion, and damage (printout etc.) by the electron beam is caused. In order to prevent this, the sample is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass therethrough. Therefore, the use of a high-pressure electron microscope enables clearer observation. From the particle photograph obtained by such a method,
The position and number of dislocation lines in each silver halide grain can be determined.

There is no particular limitation on the method of introducing dislocation lines into silver halide grains. For example, a method in which an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution are added by a double jet, silver iodide fine grains A dislocation line of a desired position and amount is introduced by a known method such as a method of adding iodine ion solution, a method of adding only an iodide ion solution, and a method of using an iodide ion releasing compound described in JP-A-6-11781. Can be.

As an embodiment of the production of the silver halide emulsion of the present invention, tabular silver halide grains serving as a base are first prepared, and the tabular silver halide grains are firstly oriented in the lateral direction. A method in which a low iodide silver halide phase is preferentially grown and then a high iodide silver halide phase is grown in the main plane direction, or conversely, first, a high iodine halide is formed in the main plane direction. The silver halide phase is preferentially grown,
Then, utilizing the method of growing a low iodide silver halide phase in the lateral direction, etc., and combining the following various methods and conditions, the composition of the extremely thin silver halide layer is precisely controlled. It is possible to use a method of forming while forming.

In order to grow tabular silver halide grains preferentially in the lateral direction or in the main plane direction, silver ions, halide ions during the growth of the silver halide grains, or halogens during the growth due to dissolution thereof. It is important to select the concentration, growth temperature, pBr, pH, gelatin concentration, etc. of the additive solution containing silver halide fine particles for supplying silver ions and halide ions to the silver halide particles. It can be controlled to some extent by the combination of the shape of the tabular substrate grains, the halogen composition, the ratio of the (100) face / (111) face of the side face, and the like.

For example, the preferred pBr for growing preferentially in the lateral direction is 1.0 to 2.5, and the gelatin concentration is 0.5 to 2.0%. In order to form high aspect ratio tabular silver halide grains not to be formed, the pH is preferably set to 2.0 to 5.0. On the other hand, the preferred pBr for growing preferentially in the main plane direction is 2.5 to 4.5.

In order to precisely and uniformly control and form the thickness of the outermost layer of silver halide crystal and the composition of silver halide,
A supply method using silver halide fine particles for supplying silver ions and halide ions to growing silver halide particles by dissolution is more suitable than a supply method using ions.

The general formula (1) used in the invention of claim 1
The compound represented by is described.

In the general formula (1), the aliphatic group represented by R ₁ and R ₂ is a straight-chain or branched alkyl or alkenyl having 1 to 30, preferably 1 to 20 carbon atoms.
Each group such as alkynyl or cycloalkyl is exemplified.
Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-
Butyl, 2-ethylhexyl, allyl, 2-butenyl,
Each group includes 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl and the like. Examples of the aromatic group represented by R ₁ and R ₂ include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R ₁ and R ₂ may be a single ring or a condensed ring, and is a 5- to 6-membered heterocyclic group having at least one of O, S and N atoms and an amine oxide group in the ring. Is mentioned.

Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan,
Examples include thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and groups derived from these benzerogues. R ₁ and R ₂ form a ring,
A 4- to 7-membered ring can be mentioned. It is preferably a 5- to 7-membered ring.

Preferred groups for R ₁ and R ₂ are a heterocyclic group and an aromatic group, more preferably a heteroaromatic group. The aliphatic group, aromatic group or heterocyclic group represented by R ₁ and R ₂ may be further substituted with a substituent, and the substituent may be a halogen atom (eg, a chlorine atom, a bromine atom, etc.). An alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group (eg, a cyclopentyl group,
Cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group) Ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, etc.), cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (E.g., methylthio, ethylthio, butylthio, etc.), arylthio (e.g., phenylthio,
p-methylphenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3- Dimethylureido group, etc.), sulfamoylamino group (eg, dimethylsulfamoylamino group, diethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, p-chlorophenoxycarbonyl Base ), A sulfonyl group (for example,
Methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy Group, nitro group, nitroso group, amine oxide group (eg, pyridine oxide group), imide group (eg, phthalimide group), disulfide group (eg, benzene disulfide group, benzothiazolyl-2)
-Disulfide group, etc.) and heterocyclic groups (eg, pyridyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). Substituents containing an electron withdrawing group are particularly preferred. R ₁ and R ₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. m is an integer of 2 to 6, preferably 2 to 3.

The following is a general formula (1) used in the present invention.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

The compound represented by the general formula (1) can be synthesized by an ordinary method well known to those skilled in the art.

The compound represented by the general formula (1) can be added and used at any stage in the production process of a silver halide emulsion, or can be added and used at any stage immediately before coating after emulsion production. Can be. The preferred addition step in the present invention is effective immediately after the completion of chemical ripening and immediately before coating. The preferable addition amount of the compound represented by the general formula (1) is 1 × 10 ⁻⁸ to 1 mol / Ag mol, more preferably 1 × 10 ⁻⁶ to 1 × 0.3 mol / Ag mol.

One feature of the invention according to claim 2 is that the sensitizing dye is added in the form of fine solid dispersion. The fine particle solid dispersion state of the sensitizing dye referred to in the present invention,
It means a solution containing a solute present as a solid phase, and refers to a solution containing mechanically dispersed solid fine particles of 1 μm or less. In order to prepare a solution containing solid fine particles of a sensitizing dye, for example, the solubility at 27 ° C. in an aqueous system free of an organic solvent and / or a surfactant is 1 × 10 ⁻⁴ to 4 × 10 ^−4.
A spectral sensitizing dye of × 10 ^-2 mol / l may be added to the dispersion medium in an amount exceeding the solubility and dispersed mechanically, as disclosed in JP-A-3-288842 and JP-A-5-297496.
And the method described in JP-A-6-186657 and the like.

The solid dispersion of the sensitizing dye in fine particles will be further described.

In the present invention, 1 μm dispersed mechanically
The following solid fine particles are those dispersed in solid fine particles having an average particle size of 1 μm or less based on a volume particle size equivalent to a sphere, and can be measured by a general method.

In the present invention, the dispersion medium preferably does not substantially contain an organic solvent and a surfactant. As used herein, the organic solvent refers to a solvent containing carbon atoms and being liquid at room temperature, and examples thereof include alcohols, ketones, nitriles, and alkoxy alcohols. Specifically, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol,
Examples include 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol, dimethylformamide and the like.

The surfactant includes an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

"Contains substantially no organic solvent or surfactant" means that it does not contain an organic solvent or surfactant in an amount that adversely affects the silver halide emulsion.

In the present invention, various dispersers are effectively used for mechanically pulverizing and dispersing the sensitizing dye in an aqueous solvent. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. In the present invention, a high-speed stirrer is preferable.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on a vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having an anchor blade is more preferable.

As a concrete working example, after water is poured into a temperature-adjustable tank, a certain amount of the powder of the spectral sensitizing dye is added, and the mixture is stirred for a certain period of time by a high-speed stirrer under temperature control. Then crush and disperse. The pH and temperature at the time of mechanically dispersing the spectral sensitizing dye are not particularly limited. However, at low temperatures, the dispersion does not reach a desired particle size even after long-time dispersion, and at high temperatures, reaggregation or decomposition occurs. And the problem that desired photographic performance cannot be obtained, and that when the temperature is increased, the viscosity of the solution system decreases, so that the efficiency of pulverization and dispersion of solids is greatly reduced. Therefore, dispersion temperature 15 ~
The temperature is more preferably 50 ° C. Further, the stirring rotation speed at the time of dispersion requires a long time to obtain a desired particle size at a low rotation speed, and bubbles are entrained at a high rotation speed to lower the dispersion efficiency. Is more preferable.

The sensitizing dyes preferably used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonols, merostyril and strepto dyes. Examples thereof include polymethine dyes containing cyanine.
Particularly effective sensitizing dyes include sensitizing dyes belonging to cyanine dyes, merocyanine dyes, complex cyanine dyes and complex merocyanine dyes. The above sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. You may.

The addition amount of such a sensitizing dye largely depends on the type of silver halide emulsion. In the case of a normally preferred silver halide size of 0.2 to 1.5 μm, 1 to 1 mol per mol of silver halide is required. It is preferably from × 10 ^-6 to 1 × 10 ^-4 mol.

Next, the coagulated polymer used in the desalting step of the silver halide emulsion according to the third aspect of the present invention will be described.

The term "aggregated polymer agent" as used in the present invention means a polymer substance capable of coagulating silver halide grains together with a protective colloid.

As the aggregating polymer, a modified gelatin obtained by substituting 50% or more of amino groups of a gelatin molecule can be preferably used. Hereinafter, this may be also referred to as a G agent. Examples of substituents for the amino group of gelatin are described in U.S. Pat. Nos. 2,691,582 and 2,614,928;
No. 2,525,753.

Examples of useful substituents for obtaining a modified gelatin by substituting an amino group include (1) an acyl group such as alkylacyl, arylacyl, acetyl and substituted or unsubstituted benzoyl, (2) an alkylcarbamoyl, Carbamoyl groups such as arylcarbamoyl, (3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl, (4)
Thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl; (5) linear or branched alkyl groups having 1 to 18 carbon atoms; (6) substituted and unsubstituted phenyl, naphthyl and pyridyl, furyl and other aromatic heterocyclic groups. And an aryl group such as a ring. Among them, preferred modified gelatin is one derived from an acyl group (—COR ¹¹ ) or a carbamoyl group (—CONR ¹¹ R ¹² ).

R ¹¹ is a substituted or unsubstituted aliphatic group (eg, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group or an aralkyl group (eg, a phenethyl group); R ¹² is a hydrogen atom; It is an aliphatic group, an aryl group, or an aralkyl group. Particularly preferred is a case where R ¹¹ is an aryl group and R ¹² is a hydrogen atom.

In the following, specific examples of the G agent which can be used as the aggregating polymer agent in the present invention are exemplified by amino group substituents, but the present invention is not limited thereto. Exemplified G agent (amino group substituent):

[0074]

Embedded image

When the agent G is used for the removal (desalting) of dissolved substances, the amount thereof is not particularly limited, but is 0.1 to 5 times the substance (preferably gelatin) contained as a protective colloid at the time of removal. The amount (weight) is generally suitable, particularly preferably 0.3 to 2 times (weight).

In the present invention, in order to coagulate the silver halide emulsion, the aggregating polymer may be added to the silver halide emulsion as a solid and dissolved therein. Conveniently, it is added as an aqueous solution of less than 10%.

Preferred examples of the aggregating polymer agent include a polymer compound represented by the following general formula (A) comprising the following A chain and B chain.

[0078]

Embedded image

In the formula, R ₁ and R ₂ represent an aliphatic group, which may be different from each other or may be the same. R ₃ represents a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group. X is -O
-, -NH-, and M ⁺ represent a cation. n is 10
Take a value of 10 ⁴ . The two connecting hands of the B chain are A
Either side may be linked to the tertiary carbon to which R ₁ and R ₂ of the chain are arranged. Also when X is -NH- may form a nitrogen-containing ring together with R _3.

This polymer compound has a molecular weight of preferably 10 ³ to 10 ⁶ , more preferably 3 × 10 ³ to 2 × 1.
0 is ^5, the protective colloid addition amount contained in the emulsion (preferably gelatin) preferably in a weight ratio with respect to 1 /
It is 50 to 1/4, more preferably 1/40 to 1/10. The method of use is in accordance with the above-mentioned agent G.

Specific examples of the polymer compound represented by the general formula (A) (hereinafter, this may be also referred to as P agent) are shown below, but are not limited thereto.

Illustrative P agent represented by formula (A):

[0083]

Embedded image

[0084]

Embedded image

The feature of the present invention is that the pH of the silver halide emulsion is kept at 5.1 or less throughout the desalting step. In particular, when the pH is maintained at 4.9 to 4.1, favorable flocking occurs and an emulsion with low fog can be obtained.

The desalting step referred to here is a step from the time when a flocculant is added to the silver halide emulsion in order to remove dissolved substances such as soluble salts from the silver halide emulsion formed in the presence of the protective colloid. This refers to a process from the completion of removal of a supernatant containing soluble salts and the like after one or several times of coagulation and sedimentation.

An acid is generally used for pH adjustment, and organic acids such as acetic acid, citric acid, and salicylic acid, hydrochloric acid, nitric acid, and the like are used.
Inorganic acids such as sulfuric acid, phosphoric acid and the like are preferably used, and among them, citric acid is particularly preferable because of the preferred setting.

Further, the present invention is characterized in that the temperature of the silver halide emulsion when the flocculant is added is kept at 40 ° C. or higher. Particularly, when the temperature is maintained at 53 to 75 ° C., preferable stiffening can be performed.

Next, one feature of the silver halide color photographic light-sensitive material according to the fourth aspect of the invention is that it contains a compound represented by the general formula (2).

In the general formula (2), examples of the alkyl group represented by R ₃ and R ₄ include, for example, methyl, ethyl,
Examples include propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, and the like. These alkyl groups further include a halogen atom (eg, chlorine, bromine, fluorine, etc.) and an alkoxy group (eg, methoxy, ethoxy,
1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy groups (eg, phenoxy, naphthyloxy, etc.), aryl groups (eg, phenyl, naphthyl, etc.), alkoxycarbonyl Groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl groups (eg, vinyl, allyl) Etc.), a heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, selenazolyl, sulfolanyl, piperidinyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl) Pyrazinyl, pyrimidinyl,
Groups such as pyridazinyl, pyrimidyl, pyrazolyl, and furyl), alkynyl groups (eg, groups of propargyl),
An amino group (e.g., amino, N, N-dimethylamino,
Each group such as anilino), a hydroxy group, a cyano group, a sulfo group, a carboxy group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) You may.

The alkenyl groups represented by R ₃ and R ₄ include, for example, vinyl and allyl, the alkynyl group includes, for example, propargyl, and the aryl group includes, for example, phenyl, naphthyl and the like. Examples of the heterocyclic group include, for example, a pyridyl group (for example, each group such as 2-pyridyl, 3-pyridyl, and 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a phenyl group, and a pyrrolyl group. Group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group,
And a tetrazolyl group.

The above-mentioned alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted by the same groups as the alkyl groups represented by R ₃ and R ₄ and the substituents of the alkyl groups. it can.

Hereinafter, specific examples of the compound represented by the formula (2) will be shown, but the present invention is not limited thereto.

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

The compound represented by the general formula (2) can be synthesized by an ordinary method well known to those skilled in the art.

The present invention is characterized in that the compound of the general formula (2) is added between the addition of the spectral sensitizing dye and the chalcogen sensitizer. In the present invention, the timing of addition refers to the time when spectral sensitization and chemical sensitization additives are added. In the present invention, the compound of the general formula (2) is added during the respective addition periods of the spectral sensitizing dye and the chalcogen sensitizer, thereby limiting the chemical sensitizing site of the silver halide grains and efficiently increasing the chemical sensitizing sites. Sensitivity can be increased.

The chalcogen sensitizer according to the present invention refers to a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer well known in the art. The chalcogen sensitizer is added to a solution containing silver halide grains during chemical sensitization, and causes a decomposition reaction on the surface of the silver halide grains, and in the case of a sulfur sensitizer, a sulfur element,
In the case of a selenium sensitizer, selenium element is released, and in the case of tellurium sensitizer, tellurium element is released. The (111) reactive chalcogen sensitizer is a sensitizer in which the decomposition reaction rate on the (111) plane is higher than the decomposition reaction rate on the (100) plane, the temperature during chemical ripening, and the temperature in the reaction mother liquor. Under the conditions of silver concentration and pH, the reaction rate of the decomposition reaction on the (111) plane is (10).
0) By using a sensitizer larger than the decomposition reaction rate on the surface and a compound adsorbed on silver halide grains,
A chalcogen sensitizer whose reaction rate on the surface is higher than that on the (100) surface. The ratio of the reaction rate on the (111) plane to the reaction rate on the (100) plane is preferably 3 or more, more preferably 5 or more.

One of the chalcogen sensitizers in the present invention is a sulfur sensitizer. Specifically, 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-
Preferred are thiourea derivatives such as thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, organic polysulfide compounds, thiosulfates, and simple sulfur. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.
In addition, U.S. Patent Nos. 1,574,944 and 2,41
No. 0,689, 2,278,947, 2,72
8,668, 3,501,313, 3,65
6,955, etc., West German Application Publication (OLS)
No. 1,422,869, JP-A-56-24937, and JP-A-55-45016 can be used.

As the selenium sensitizer which is a chalcogen sensitizer used in the present invention, an unstable selenium compound which can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Pat. No. 1,574,944
No. 1,602,592, 1,623,499
JP-A-60-150046, JP-A-4-2583
2, No. 4-109240, and No. 4-147250.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (for example, dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, trifurylphosphine selenide, tripyridylphosphine selenide, etc.) are exemplified. Particularly preferred selenium sensitizers are selenoureas, selenamides, selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. US Patent 1,57
4,944, 1,602,592, 1,62
No. 3,499, No. 3,297,466, No. 3,29
7,447, 3,320,069, 3,40
8,196, 3,408,197, 3,44
2,653, 3,420,670 and 3,59
1,385, French Patent 2,693,038,
2,093,209, JP-B-52-34491,
Nos. 52-34492, 53-295, 57-2
No. 2090, JP-A-59-180536 and JP-A-59-1
Nos. 85330, 59-181337, 59-18
Nos. 7338, 59-192241, 60-150
No. 046, No. 60-151637, No. 61-2467
No. 38, JP-A-3-4221 and JP-A-3-24537,
3-1-111838, 3-116132, 3-
148648, 3-237450, 4-168
No. 38, No. 4-25832, No. 4-32831, No. 4-96059, No. 4-109240, No. 4-14
No. 0738, No. 4-140739, No. 4-14725
No. 0, No. 4-184331, No. 4-190225,
Nos. 4,191,729 and 4,195,035, British Patent Nos. 255,846 and 861,984.
E. FIG. The Journal of Pho by Spencer et al.
topographic Science, Vol. 31, 15
8 to 169 (1983). It is also preferable to use a selenium sensitizer and a sulfur sensitizer in combination.

The amount of the chalcogen sensitizer added in the present invention varies over a considerable range depending on various conditions such as pH, temperature, size of silver halide grains and the like. 1 × 10 ^-1 to 1 × 10 ^-7 per
Molar is preferred.

In the present invention, furthermore, Research
It is preferable to use a noble metal salt such as gold, platinum, palladium or iridium described in Disclosure, Vol. 307, No. 307105, etc., and it is particularly preferable to use a gold sensitizer in combination. Useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like.
U.S. Pat. Nos. 2,597,856 and 5,049,48
5, JP-B-44-15748, JP-A-1-1475
And organic gold compounds disclosed in JP-A Nos. 37 and 4-70650. When a sensitization method using a gold complex salt is performed, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, or thioether as an auxiliary agent, and particularly preferable to use a thiocyanate. .

The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like, but is usually 1 × 1 per mol of silver halide.
It is preferably 0 ^-4 to 1 × 10 ^-8 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-8 mol.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers can be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by adding them to a gelatin solution in advance. The method of mixing and adding may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

In the present invention, it is also possible to use a reduction sensitizer in combination.
Sure Magazine, Vol. 307, No. 307105, and JP-A-7-786
No. 85 or the like can be used.

Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.), polyamine compounds (eg, , Diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid etc.), sodium sulfite, aldehyde compounds, hydrogen gas and the like. Japanese Patent Application Nos. 8-277938 and 8-25148
No. 6, No. 8-182,035, etc.
Alternatively, reduction sensitization may be performed in an atmosphere containing silver ions in excess.

In the silver halide emulsion according to the fifth aspect of the present invention, 1 × of alkaline earth metal per mole of silver halide is used.
^10-4 and characterized in that it contains at to 1 × 10 ^-2 mols, preferably 1 × 10 ^-4 to 5 × 10 ^-3 mol, more preferably 2 × 10 ^-4 to 2 × 10 ^{- 3} moles. As the kind of alkaline earth metal, calcium and magnesium are preferable, and it is preferable to add as a metal salt such as calcium chloride.

The alkaline earth metal can be added and used in any step of the production process of the silver halide light-sensitive material, but is preferably used at any stage immediately before the application of the silver halide light-sensitive material, and more preferably the halogenation metal is preferably used. It is to be added before the completion of spectral sensitization and chemical sensitization of the silver emulsion.

In the present invention, regarding the silver halide emulsion, in addition to the above, Research Disclosure
ureNo. 308119 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[Items] [Page RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Section crystal wall Normal crystal 999 IA Section crystal wall twin 993 IA section Epitaxial 933 Item IA Halogen composition uniform 993 IB Item Halogen composition is not uniform 993 IB Item Halogen conversion 994 IC Item Halogen substitution 994 IC Item Metal-containing 994 ID Item Monodispersion 975 IF Item Solvent addition 995 I-F Latent image forming position Surface 995 I-G Latent image forming position Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Emulsion In the present invention, physical ripening, chemical ripening and spectral sensitization are carried out with respect to the silver halide emulsion in Section 995 IJ and Section 995 II-A. To use those were. The additives used in such a process are Research
DisclosureNo. 17643, no. 187
16 and No. 308119 (hereinafter referred to as RD17
643, RD18716 and RD308119)
It is described in. The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23 to 24 648 to 649 H, I, J section Supersensitizer 996 IV-AE, J section 23-24 648-649 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known examples usable in the present invention. The photographic additives described in the above Res.
ear Disclosure.
The relevant sections are described below.

[Item] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J Item 25 Brightener 998 V 24 UV absorber 1003 VIII-I, XIII -C section 25-26 Light absorber 1003VIII 25-26 Light scattering agent 1003VIII Filter dye 1003VIII 25-26 Binder 1003IX 26 651 Static inhibitor 1006XIII 27 650 Hardener 1004X 26 651 Plasticizer 1006XII 27 650 Lubricant 1006XII 27650 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Section 1001 XXB Various couplers can be used in the present invention, and specific examples thereof are described above in Research Di. cl
osure. The relevant sections are described below.

[Item] [RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E The additives used in the present invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

The silver halide light-sensitive material of the present invention can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119VII-K.

The silver halide light-sensitive material of the present invention has the above-mentioned R
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in D308119VII-K can be employed.

To develop the silver halide light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The
Theory of The Photographic
Process Forth Edition) 2
Pages 91-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical Soc
iey) Developers known per se described in Vol. 73, 3, page 100 (1951) can be used, and the aforementioned RD17643, pages 28 to 29, R.
The development can be carried out by a usual method described in D18716, page 615 and RD308119XIX.

[0124]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these embodiments.

Example 1 (Preparation of seed emulsion T) Seed emulsion T having two parallel twin planes was prepared by the following method.

(E-1 solution) Deionized alkali-treated gelatin (weight average molecular weight 15,000) 244.0 g Potassium bromide 156.6 g 10% methanol solution of surfactant (EO-1) 0.48 ml with distilled water Finished to 34.0 L.

EO-1: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (F-1 solution) Silver nitrate 1200 g Distilled water was used to make up to 3716 ml.

(G-1 solution) Deionized alkali-treated gelatin (weight average molecular weight: 15,000) 31.6 g Potassium bromide 906.0 g Finished to 4.0 L with distilled water.

(H-1 solution) Ammonia water (28%) 299 ml (I-1 solution) Ossein gelatin 400.0 g Finished to 4832 ml with distilled water.

(J-1 solution) 69.2 g of potassium bromide The solution was made up to 386 ml with distilled water.

(K-1 solution) A 56% by weight acetic acid aqueous solution 1000 ml Using a stirring device described in JP-A-62-160128,
The solution F-1 and the solution G-1 were added to the solution E-1 which was vigorously stirred at 30 ° C. by the double jet method in 2 minutes to produce silver halide nuclei.

Thereafter, the solution I-1 was added, the temperature was raised to 68 ° C. over 41 minutes, and the solution H-1 was further added and ripened for 5 minutes. Thereafter, J-1 solution was further added, and 1 minute later, K-
The pH was adjusted to 4.7 using one solution, and the solution was immediately desalted to prepare Seed Emulsion T.

When the obtained seed emulsion T was observed with an electron microscope, the average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other was 0.31 μm, and the grain size distribution was 16%.
Was obtained.

[Preparation of Emulsion EM-1] Emulsion EM-1 was prepared using the following solutions.

(H-2 solution) Ossein gelatin 223.6 g 10% methanol solution of surfactant (EO-1) 3.6 ml Seed emulsion T 0.774 mol equivalent Distilled water was used to make 5904 ml.

(Solution I-2) 3.5 mol / L aqueous silver nitrate solution 6490 ml (Solution J-2) 3.5 mol / L aqueous potassium bromide solution 7500 ml (Solution K-2) 3.0% by weight of gelatin and iodine Fine grain emulsion consisting of silver iodide fine grains (average grain size: 0.05 μm) (Preparation method is shown below) Required amount (Preparation method of silver iodide fine grains) 6.0% by weight gelatin containing 0.06 mol of potassium iodide 5000 ml of solution
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added at a constant speed over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. The finished weight was 12.53 kg.

(Liquid L-2) 1.75 mol / L aqueous solution of potassium bromide Required amount (Liquid M-2) 56% by weight acetic acid aqueous solution Required amount (N-2 liquid) 3.5 mol / L aqueous potassium bromide solution Add the H-2 solution into a 500 ml reaction vessel and, with vigorous stirring,
Solution I-2, Solution J-2 and Solution K-2 were added by the simultaneous mixing method in accordance with the combinations shown in Table 1, seed crystals were grown, and a core / shell type silver halide emulsion was prepared.

Here, the addition rates of the liquids I-2, J-2, and K-2 were changed in a function with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

In the crystal growth, the first addition was carried out while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then reducing the solution temperature in the reaction vessel to 60 ° C. in 15 minutes. Solution N-2 was added over 4 minutes, and solution K-2 was added in an amount corresponding to 2% of the total silver used, followed by a second addition. The second addition was performed while controlling the solution temperature in the reaction vessel to 60 ° C., the pAg to 9.8, and the pH to 5.8. pA
For control of g and pH, if necessary, L-2
Solution M-2 was added.

After the completion of the above-mentioned grain growth, JP-A-58-14
After desalting according to the method described in No. 0322, gelatin was added and dispersed.
Ag was adjusted to 80 mV to obtain emulsion EM-1.

When the silver halide grains in this emulsion were observed with an electron microscope, they were hexagonal tabular monodispersed silver halide grains having an average particle size of 1.30 μm and a particle size distribution of 17% and an average aspect ratio of 8.0. there were. The tabular silver halide grains had dislocation lines on the outer periphery.

[0142]

[Table 1]

[Preparation of Emulsion EM-2] In the preparation of Emulsion EM-1, after desalting, gelatin was added and dispersed.
The emulsion EM-2 was obtained in the same manner as in EM-1 except that the pH was adjusted to 5.80 and the EAg to 50 mV.

[Preparation of Emulsion EM-3] In the preparation of Emulsion EM-1, the above-mentioned G
-15 denatured gelatin having a 90% substitution ratio
1345 ml of a weight% aqueous solution was added and stirred for 3 minutes.
Thereafter, a 73% by weight aqueous solution of citric acid was added to adjust the pH of the emulsion to 4.7, and the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
At this time, the pH of the silver halide emulsion was kept at 4.6.
Further, 15 liters of distilled water at 40 ° C. was added, and the mixture was stirred for 5 minutes, allowed to stand for 15 minutes, and the supernatant was drained by decantation. At this time, the pH of the silver halide emulsion was kept at 4.5.

Then, gelatin was added and dispersed, and EM-3 was obtained in the same manner as EM-1 except that the pH was adjusted to 5.80 and the EAg to 50 mV at 40 ° C.

Each of the emulsions thus obtained was subjected to chemical sensitization and spectral sensitization in the following manner.

<< Chemical Sensitization and Spectral Sensitization Treatment of Emulsion >> (Preparation of Emulsion A) A part of the emulsion EM-1 was heated and dissolved at 55 ° C., and 4 parts of the sensitizing dye SD-6 was added per mole of silver halide.
× 10 ^-4 mol, 1% each of SD-7 at 8 × 10 ^-5 mol
Added as a methanol solution and after 20 minutes, sodium thiosulfate pentahydrate 5.0 × 10 ⁻⁶ mol, triphenylphosphine selenide 1.5 × 10 ⁻⁶ mol, chloroauric acid 3.2 ×
A mixture of 10 ⁻⁶ mol and 3.5 × 10 ⁻⁴ mol of potassium thiocyanate was added at intervals of 2 minutes, and the sensitivity was increased in 1/100 sec.
Aged to optimize fog relationships. At the end of ripening, the stabilizer ST-1 was added, the temperature was lowered, and the mixture was cooled and solidified to obtain Emulsion A.

(Preparation of Emulsion B) Emulsion B was obtained in the same manner as Emulsion A except that Emulsion EM-2 was used.

(Preparation of Emulsion C) At the end of ripening, Exemplified Compound 1-6 of the present invention was added in an amount of 1.2 × 1 per mol of silver halide.
Emulsion C was obtained in the same manner as Emulsion B except that ^0-4 mol was added.

(Preparation of Emulsion D) In Emulsion B, the same amount of the sensitizing dye as described above was added in powder form to an appropriate amount of water previously adjusted to 27 ° C., and then added with a high-speed stirrer (dissolver).
Stirring at 00 rpm for 30-120 minutes,
Emulsion D was obtained in the same manner as Emulsion B except that it was added as a 1% sensitizing dye solid dispersion having an average particle size of 0.38 μm.

(Preparation of Emulsion E) Emulsion E was obtained in the same manner as Emulsion A except that Emulsion EM-3 was used.

(Preparation of Emulsion F) Emulsion B was prepared except that Exemplified Compound 2-23 of the present invention was added 5.0 × 10 ^-5 mol per mol of silver halide 10 minutes before the addition of the sensitizing dye. Emulsion F was obtained in the same manner as described above.

(Preparation of Emulsion G) Emulsion B was prepared in the same manner as in Emulsion B except that Exemplified Compound 2-23 of the present invention was added 5.0 × 10 ⁻⁵ mol per mol of silver halide 10 minutes after the addition of the sensitizing dye. Emulsion G was obtained in the same manner.

(Preparation of Emulsion H) Emulsion B was prepared in the same manner as Emulsion B except that 150 mg of calcium chloride was added per mol of silver halide 15 minutes after the addition of the sensitizing dye.
Emulsion H was obtained.

(Preparation of Emulsion I) To Emulsion B, 5.0 × 10 ^-5 mol of Exemplified Compound 2-23 of the present invention was added per 1 mol of silver halide 10 minutes after the addition of the sensitizing dye, and further 5 minutes later. 1 calcium chloride per mole of silver halide
50 mg was added, and upon completion of aging, Exemplified Compound 1 of the present invention 1-
Emulsion I was obtained in the same manner as in Emulsion B except that 1.2 × 10 ^-4 mol was added per mol of silver halide.

Table 2 shows the characteristics of the chemically and spectrally sensitized emulsions prepared as described above.

[0157]

[Table 2]

To each of the emulsions thus obtained, a magenta coupler M-1 dissolved in ethyl acetate and tricresyl phosphate (OIL-1) was added as shown below, and a dispersing aid (SU-1) was added. , A dispersion liquid emulsified and dispersed in an aqueous solution containing gelatin, a spreading agent (SU-2) and a hardening agent (H-1, H-2) are appropriately added to prepare a coating solution. Samples 101 to 109 were obtained by coating and drying on an acetylcellulose support by a conventional method.

A method for preparing a sample coated with a single emulsion layer will be described below.

<Preparation of Coated Sample> First Layer: Green-Sensitive Silver Halide Emulsion Layer Each Emulsion Silver Coating Amount 1.5 g / m ² M-1 0.33 g / m ² OIL-1 0.50 g / m ² Gelatin 3.5 g / m ² Second layer: Surface protective layer PM-1 0.15 g / m ² PM-2 0.04 g / m ² Gelatin 0.65 g / m ²

[0161]

Embedded image

[0162]

Embedded image

The sample obtained as described above was
Using a 0 ° K light source, a glass filter Y-4 manufactured by Toshiba Corporation
8 and a wedge exposure was performed, and color development processing was performed according to the following processing steps.

Next, the density of the dye image obtained by the color development was measured for magenta density using a densitometer manufactured by X-rite to obtain a D-LogE characteristic curve. Lowest density (fog) on the obtained D-LogE characteristic curve +
The reciprocal of the exposure amount giving a density of 0.15 was calculated and defined as the sensitivity. The relative sensitivity of each sample was determined by setting the sensitivity of the sample 101 to 100.

Further, in order to evaluate fog generated during storage, the sample was conditioned at 23 ° C. and RH 65% for 24 hours, sealed in a resin can for film, and then dried at 55 ° C. for 5 hours. Processing was performed for days. After each of the samples was processed together with the samples that had been refrigerated, the difference (ΔDmin) between the obtained minimum density values of the characteristic curves was evaluated as a fog fluctuation value during storage.

(Processing Step) << Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment * Color Development 2 minutes and 30 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 L, and potassium hydroxide or 20% sulfuric acid was used. And adjust the pH to 10.06.

Color developing replenisher Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 L, and adjust to pH 10.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 L, and use ammonia water or glacial acetic acid. Adjust to pH 4.4.

Bleach replenisher Water 700 ml 1,3-Diaminopropanetetraacetate iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.4 using aqueous ammonia or glacial acetic acid , Water to make 1L.

Fixer Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, water is added to make 1 L.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 L.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (L-77 manufactured by UCC) 0.1 g Ammonia water 0.5 ml After adding water to make 1 L, the pH is adjusted to 8.5 using ammonia water or 50% sulfuric acid.

Table 3 shows the evaluation results of the samples obtained as described above.

[0176]

[Table 3]

As is evident from Table 3, each sample having the constitution according to the present invention has low fog, high sensitivity, and improved fog increase during storage.

Example 2 On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to produce a multilayer color photographic light-sensitive material 201.

The amount of addition is expressed in grams per 1 m ² . However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^{-5 SD-2 2.3 × 10 -4} SD-3 4.5 × 10 -4 C-2 0.52 CC-1 0.06 DI-1 0.047 O L-2 0.46 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL- 2 0.27 AS-2 0.006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color-sensitive layer) Silver bromide a 0.19 Silver iodobromide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-3 0.05 Gelatin 0.61 Eighth layer (middle layer) OIL-1 0.26 AS-1 0.054 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL- 1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 Tenth layer (highly sensitive green color-sensitive layer) Emulsion I of the present invention prepared in Example-1 1.19 M-1 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-20 014 gelatin 1.23 eleventh layer (yellow filter layer) yellow colloidal silver 0.05 OIL-1 0.18 A S-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide g 0.09 SD-96 0.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y-1 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high sensitivity Blue-sensitive layer) Silver iodobromide g 0.41 Silver iodobromide h 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-1 0.23 OIL- 1 0.10 AS-2 0.004 Gelatin 1.20 14th layer (First protective layer) Silver iodobromide i 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0 55 the above characteristics iodobromide are listed in Table 4. In the table, the average particle size is represented by the length of one side of a cube having the same volume.

[0181]

[Table 4]

Examples of forming typical silver halide grains of the present invention are described in JP-A-1-183417 and 1-183.
No. 644, No. 1-183645, No. 2-166442
And Japanese Patent Application No. 9-9423.

In addition to the above composition, a dispersing aid SU-
1, coating aid SU-2, SU-3, SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-11 (polyvinylpyrrolidone having a weight average molecular weight of 10,000), AF-12 (weight average molecular weight: 100,
000 polyvinylpyrrolidone), hardeners H-1, H-
2 and the preservative Ase-1 were added as appropriate.

The structure of the compound used in the above sample is shown below.

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

[0193]

Embedded image

Next, the 10th sample 201
Samples 202 and 20 were prepared in the same manner except that the emulsion I of the present invention used in the layers was changed to the comparative emulsions A and B prepared in Example 1.
3 was produced. Samples 201 to 20 thus obtained
3 was subjected to color development in the same manner as in Example 1, and each performance was evaluated. The obtained results are shown in Table 5.

Note that the sensitivity is the same as the D obtained from the sample 201.
Calculating the reciprocal of the amount of exposure that gives a density of the minimum density (fog) +0.3 in the magenta density on the LogE characteristic curve, defining it as the sensitivity, and setting the sensitivity of the sample 201 as 100 and the relative sensitivity of each sample as I asked. Also, fog is
The unexposed sample is subjected to the reference color development processing, and Xr
Magenta density 1 was measured with a densitometer manufactured by ITE. Then, the color developing agent 4-amino-3-methyl-N
Preparing a color developer and a color developer replenisher excluding -ethyl-N- (β-hydroxyethyl) aniline sulfate,
Except for using this, development processing was performed in the same manner as the reference color development processing, and magenta density 2 was measured in the same manner, and substantial fog density = (magenta density 1)-(magenta density 2) was calculated. The storage stability was measured in the same manner as in Example 1.

[0196]

[Table 5]

As is clear from Table 5, Sample 201 using Emulsion I manufactured according to the constitution of the present invention was Comparative Sample 2
02 and 203, high sensitivity similar to the result of Example 1,
Low fog and excellent storage stability were obtained.

[0198]

According to the present invention, a silver halide color photographic material having high sensitivity, excellent fog stability and improved storage stability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/392 G03C 7/392 A

Claims (6)

[Claims] 1. A silver halide color photographic apparatus having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. A silver halide color photographic material comprising a compound represented by the following general formula (1) and a silver halide emulsion chemically sensitized at a silver potential of 40 to 70 mV. Formula (1) R _1- (S) m-R _{2 In the} formula, R ₁ and R ₂ are each an aliphatic group, an aromatic group, a heterocyclic group, or an atomic group capable of forming a ring by bonding to each other. Represents When R ₁ and R ₂ are an aliphatic group, they may combine with each other to form a ring. m represents an integer of 2 to 6. 2. A silver halide color photographic device having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. A silver halide color photographic light-sensitive material, characterized in that the light-sensitive material contains a silver halide emulsion which is added with a sensitizing dye in a fine solid dispersion state and has a silver potential of 40 to 70 mV and is chemically sensitized. 3. A silver halide color photographic device having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a light-sensitive material, an aggregating polymer agent is added in a desalting step, and when the processing temperature in the desalting step is 40 ° C. or more, p
H is set to 5.1 or less, and then the silver potential is set to 40 to 70 mV.
A silver halide color photographic light-sensitive material, characterized by containing a silver halide emulsion chemically sensitized in (1). 4. A silver halide color photograph having on one side on a support at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In the light-sensitive material, a compound represented by the following general formula (2) is added during the respective addition periods of the spectral sensitizing dye and the chalcogen sensitizer, and the halogenated compound is chemically sensitized at a silver potential of 40 to 70 mV. A silver halide color photographic material comprising a silver emulsion. Embedded image In the formula, X represents N or CR ', and R' represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₃ and R ₄ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n represents 0 or 1. R ₃ and R ₄ -SO ₃ H, -COOH, -OH and -NHR
₅ or directly or indirectly has at least one group selected from salts thereof. R ₅ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. 5. A silver halide color photographic having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The photosensitive material contains 1 × 10 ^-4 to 1 × 10 ^-2 mol of alkaline earth metal per mol of silver halide and contains a silver halide emulsion chemically sensitized at a silver potential of 40 to 70 mV. A silver halide color photographic light-sensitive material, characterized in that: 6. A silver halide color photograph having on one side on a support at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The light-sensitive material contains the compound represented by the general formula (1), and the compound represented by the general formula (2) is added between the addition times of the spectral sensitizing dye and the chalcogen sensitizer. A silver halide emulsion containing 1 × 10 ^-4 to 1 × 10 ^-2 moles of alkaline earth metal per mole of silver halide and chemically sensitized at a silver potential of 40 to 70 mV. Silver halide color photographic light-sensitive material.